Carbamate condensation method and unit for carrying out such a method

ABSTRACT

Method for carbamate condensation of a carbon dioxide/ammonia gaseous phase in a liquid phase in a condensation unit of the so-called submerged type comprising a heat exchange tube bundle having a predetermined number of tubes intended for carbamate condensation, wherein the gaseous phase and the liquid phase are fed contemporaneously and independently to each of the tubes intended for condensation.

FIELD OF APPLICATION

The present invention relates to a method for carbamate condensation ina unit of the so-called submerged type, used in a plant for theproduction of synthesis urea from gaseous carbon dioxide and liquidammonia.

The present invention also relates to a carbamate condensation unit forcarrying out the above method

Prior Art

In order to produce urea, the reactants, i.e. carbon dioxide andammonia, are fed partially condensed in form of carbamate in a synthesisreactor, wherein the condensation of carbamate, an intermediate productof the synthesis, is carried out to an almost complete extent. Only aportion of the carbamate is then converted into urea in the reactoritself, by virtue of the chemical balances that characterize thisconversion.

The remaining portion of unconverted carbamate, together with theunreacted ammonia, is then forced out of the reactor and at leastpartially recovered, by stripping, for example with CO₂, in form ofgaseous ammonia and carbon dioxide by per se known processes.

These gaseous compounds must then be partially condensed, thus obtainingtheir conversion into liquid carbamate that is then recycled to thesynthesis reactor.

As known, in a plant for urea production, it is required to convertthrough condensation into carbamate part of the reactants and of theintermediate products that, unconverted into urea in the synthesisreactor, are recovered downstream thereof in form of gaseous ammonia andcarbon dioxide.

In order to satisfy the aforesaid requirement, in EP-A-1 036 787 acondensation unit of the so-called submerged type has been proposed,comprising a cylindrical shell inside which is supported a tube bundle,wherein the tubes are straight and in heat exchange relationship with asuitable coolant.

In the tube bundle, with the tubes full of liquid (submerged), ammoniaand carbon dioxide condensation takes place, together with theirreaction to form carbamate.

Although advantageous as far as some aspects thereof are concerned, thecondensation unit exhibits a remarkable drawback that will be describedhereinbelow.

In fact, it has been found out that, contrary to the expected designoperation, only a minor portion of the tubes of the tube bundle intendedfor condensation are indeed used for the conversion into carbamate ofthe gaseous compounds flowing from a lower end to an upper end thereof.The remaining major portion of such tubes of the tube bundle are on thecontrary flown by the liquid phase only and in part used for the recycleof a portion of the condensed gaseous compounds from the upper end tothe lower end of the tube bundle. In other words, it has been found outthat the gaseous compounds flow within the tube bundle throughoutpreferential paths of heterogeneous reactant concentration definedwithin a very limited number of tubes.

Since, given a tube bundle of predetermined size, the yield isstrictly-bound to the only part thereof intended for the condensation(i.e. flown by the gaseous compounds), the presence of a relevantportion of tubes intended for condensation flown by the liquid phaseonly, drastically reduce the condensation yield of the condenser.Moreover, it also negatively affects the natural circulation of theliquid phase inside the condenser thus decreasing the efficiency of theapparatus.

SUMMARY OF THE INVENTION

The technical problem underlying the present invention is that ofproviding a method for carbamate condensation in a unit of the so-calledsubmerged type, wherein the efficiency and the condensation yield areremarkably increased with respect to the teaching of the prior art.

According to the present invention, this problem is solved by a methodfor carbamate condensation of a carbon dioxide/ammonia gaseous phase ina liquid phase in a condensation unit of the so-called submerged typecomprising a heat exchange tube bundle having a predetermined number oftubes intended for carbamate condensation,

characterized by the step of:

-   -   feeding, contemporaneously and independently, said gaseous phase        and said liquid phase within each of said tubes intended for        condensation.

Thanks to the present invention, it is possible to effectively use alltubes of the tube bundle intended for condensation to convert intocarbamate the gaseous compounds. In fact, the step of feeding separatelyand independently the gaseous phase and the liquid phase, respectively,to each single tube intended for condensation, allows advantageously touniformly and homogenously distributing the gaseous compounds within allof such tubes.

In this respect, it should also be noted that with the present method,the condensation reaction is carried out within each of the tubesintended for condensation at substantially the same operatingconditions, to all advantage of the heat exchange coefficient and of thecondensation yield.

As the tubes of the tube bundle intended for condensation are indeedused to carry out the condensation, the method of the present inventionallows advantageously to obtain an efficiency and a condensation yieldof the condensation unit which substantially corresponds to the designone.

Further features and advantages of the present invention will appearmore clearly from the following non-limiting description of anembodiment thereof, made with reference to the attached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings:

FIG. 1 shows a schematic view in longitudinal section of a condensationunit for carrying out the method according to the present invention;

FIG. 2 shows a schematic view in longitudinal section of a detail of thecondensation unit according to FIG. 1;

FIG. 3 shows schematic view in longitudinal section of a furtherembodiment of the condensation unit for carrying out the methodaccording to the present invention;

FIG. 4 shows a schematic view in longitudinal section of a detail of thecondensation unit according to FIG. 3.

DETAILED DESCRIPTION OF THE DRAWINGS

With reference to FIGS. 1 and 2, with 1 is globally indicated acondensation unit for carrying out the method according to the presentinvention comprising a cylindrical shell 2 closed at the opposed ends byan upper bottom 3 and a lower bottom 4, respectively.

In the shell 2 a tube bundle 5 is supported having a predetermined size,i.e. having a predetermined number of straight tubes 6 of predeterminedlength and diameter, said straight tubes 6 being supported by opposedupper and lower tube plates 7, 8, respectively. Said plates 7 and 8separate the shell 2, which defines an intermediate portion 9 of thecondensation unit, from the bottoms 3 and 4, which define an upperportion 10 and a lower portion 11 of the condensation unit 1,respectively.

Said portions 10 and 11 are reciprocally in fluid communication throughthe plurality of straight tubes 6 of the tube bundle 5. The tubes 6 aregrouped in tubes 6′ intended for carbamate condensation at theirinternal and in tubes 6″ intended for recycle of a portion of thecondensed gaseous compounds from the upper portion 10 to the lowerportion 11 of the condensation unit 1.

It should be noted that said tube bundle 5 is in heat exchangerelationship with a coolant, for example water, flowing outside thetubes 6 (shell side) and fed into the condensation unit and exitingtherefrom through suitable openings and connecting means that are notshown as per se conventional.

The upper portion 10 of the condensation unit is provided with a firstgas discharge opening 12, formed in the upper bottom 3 and with secondopenings 13 formed in the side part of the portion itself.

In said portion 10, and in proximity to said second openings 13,overflow devices 14 are provided, which are schematically illustrated bya baffle.

The lower portion 11 is provided with a first opening 15 to which passesa first duct 16 fastened thereto, for feeding the gases to be condensed,and a second opening 19 for feeding the liquid phase, as will be clearin the following description.

Said first duct 16 has a free end 17, located inside a gas distributionchamber 18, supported in a conventional manner inside said lower portion11 of the condensation unit. The distribution chamber 18 comprises aperforated wall 18 a a provided proximate to the lower tube plate 8.

According to the present invention, and as better shown in the detail Aof FIG. 2, the condensation unit 1 comprises a plurality of connectingducts 21 extending from the gas distribution chamber 18 to the internalof the tubes 6′ intended for condensation, so as to obtain a direct gascommunication between said chamber and said tubes. For simplicity ofpresentation, in FIG. 1, ducts 21 are only randomly and schematicallyshown and do not reflect the actual number and position of such ductsrepresented in the detail of FIG. 2.

In particular, the connecting ducts 21 pass through and are fastened toopenings 20 of the perforated wall 18 a and have a free upper end 21 aending within and in proximity of a lower end 6 a of the tubes 6′intended for condensation.

Preferably, the upper end 21 a of the connecting ducts 21 has a diameterslightly smaller than the diameter of the lower end 6 a of the tubes 6′intended for condensation, so that an annular space 22 is definedbetween ducts 21 and tubes 6′ for the inlet thereto of the liquid phase.

With reference to the condensation unit 1 of FIGS. 1 and 2, it is nowdescribed an example of implementation of the carbamate condensationmethod according to the present invention. In these figures, Fg and Flgenerally indicate the flows of the gaseous phase and of the liquidphase inside the condensation unit 1, respectively, while Fg+Flindicates a mixed gaseous/liquid phase flowing within the tubes 6′intended for condensation. Moreover, Fc further schematically indicatesthe flow of a coolant fed to the condensation unit 1 and withdrawntherefrom.

With reference to FIG. 1, the volume of the condensation unit 1,schematically illustrated when in regular operation, is entirely takenup by the liquid phase, that is an aqueous solution comprisingcarbamate, ammonia and optionally urea, and by the gaseous phase, thatis gaseous compounds comprising ammonia, carbon dioxide and generallywater in the form of vapors.

Said gaseous compounds in a vapor phase come from a stripping unit (notshown) downstream a synthesis reactor (not shown) for the decompositionof carbamate and the ammonia and carbon dioxide stripping from the ureasolution coming from the synthesis reactor. These compounds are fed intothe condensation unit by the above said first feeding duct 16 andcollected in the gas distribution chamber 18 within the lower portion11.

At the same time, a flow comprising carbamate in aqueous solution comingfrom a urea recovery section (not shown), and optionally a solutioncomprising urea and unreacted substances coming from the synthesisreactor (not shown) and feed liquid ammonia, are fed in the lowerportion 11 of the condensation unit 1 through the second opening 19.

Advantageously, according to the present method, the liquid phase andthe gaseous phase are fed contemporaneously and independently withineach of said tubes 6′ intended for condensation, so that gas and liquidare first contacted and mixed for reaction and condensation of thegaseous reactants to carbamate in such tubes 6′, only. In other words,there is no mixing of these two phases in the lower portion 11, betweenthe gas distribution chamber 18 and the lower tube plate 8.

To this aim, said gaseous phase is made to flow from the distributionchamber 18 to the internal of the tubes 6′ intended for condensation, inthe proximity of their lower end 6 a, through the connecting ducts 21;while the liquid phase flows from the second opening 19 around the gasdistribution chamber 18 and enters the tubes 6′ through the annularspaces 22 defined between ducts 21 and tubes 6′.

Inside said tube 6′, the two phases are mixed together and ammonia,carbon dioxide and water first condensate and then ammonia reacts withcarbon dioxide, thus forming carbamate.

This carbamate is added to the carbamate already present in the aqueoussolution inside the condensation unit 1, obtaining in this way, at theoutlet of the tubes 6′, one carbamate solution possibly comprising alsourea.

The carbamate solution flows in the upper portion 10, wherein a firstpart thereof is recycled to the lower portion 11 through the ducts 6″,and a second part thereof exits the unit 1 through the openings 13 witha flow regulated by the overflow devices 14. The portion of solutionexiting the unit 1 through the openings 13 is then sent to the synthesisreactor for the conversion into urea of the carbamate and ammoniatherein contained.

It should be noted that the ducts 6″ provide the circulation of theliquid phase inside the condensation unit 1, in particular from theupper portion 10 of the condensation unit 1 to its lower portion 11.

Thanks to the features of the present invention, it is possible tohomogenously and uniformly distribute the gaseous compounds within alltubes 6′ of the tube bundle 5 intended for condensation, avoiding theformation of undesired preferential paths of gas phase, thus exploitingthe tube bundle 5 according to its design operation.

It follows that the condensation yield and the efficiency of thecondensation unit 1 are substantially improved with respect to the priorart. In fact, it is now possible to carry out the carbamate condensationreaction within each of the tubes 6′ intended for condensation atsubstantially the same operating conditions. This also positively affectthe natural circulation of the liquid phase within the unit 1, whichguarantees that the tubes 6′ intended for condensation are always fullof solution and contain a constant amount thereof and allows an optimalcrossing speed through the tubes 6′ to be maintained by the liquid phaseto all advantage of the heat exchange between said liquid phase and thecoolant flowing outside the tubes, and therefore of an effectivecondensation of the gaseous compounds.

Should any gaseous substance be still present in the upper portion 10,they will be vented from the condensation unit 1 through the opening 12provided in the upper bottom 3.

The synthesis reactor, the stripping unit and the condensation unit 1are all part of the so-called high-pressure synthesis loop of plant forthe industrial production of urea. Such apparatuses do in fact operatesubstantially at the same pressure and are connected the one to theother in order to make possible the separation and recycle to thesynthesis reactor of at least a portion of the unreacted substancescontained in the urea solution coming out therefrom.

The above described carbamate condensation method and unit 1 forcarrying out such a method are subject to modifications and changes.

Thus, an alternative embodiment of the invention is for example shownwith reference to FIGS. 3 and 4.

In this figures, the details of the condensation unit 1 that arestructurally and functionally equivalent to those illustrated in FIGS.1-2 will be indicated with the same reference numbers and will not bedescribed any more.

According to this embodiment, the carbamate condensation unit 1comprises a further gas distributor chamber, generally indicated byreference 23, supported in a conventional manner inside said lowerportion 11 above the gas distribution chamber 18 and of substantiallythe same shape.

The further chamber 23 is advantageously divided in a plurality ofsectors 24 (six in the example of FIG. 3), contiguous, but slightedseparated the one from the other so as to define intermediate channels25 for the passage of the liquid phase between the sectors 24.

The sectors 24 are closed at their top by a perforated wall 24 aprovided in the close proximity of the lower tube plate 8.

According to the present embodiment of the invention, and as bettershown in the detail B of FIG. 4, the connecting ducts 21 now extend fromthe sectors 24 of the further gas distribution chamber 23 to theinternal of the tubes 6′ intended for condensation, so as to obtain adirect gas communication between said further chamber and said tubes.For simplicity of presentation, in FIG. 3, ducts 21 have not been shown.

In particular, the connecting ducts 21 pass through and are fastened toopenings 26 of the sector perforated wall 24 a and have the free upperend 21 a ending within and in proximity of the lower end 6 a of thetubes 6′ intended for condensation.

With reference to the embodiment of FIGS. 3 and 4, the implementation ofthe carbamate condensation method according to the present inventionsubstantially corresponds to that described with respect to FIGS. 1-2,with the exception that: the gaseous compounds leave the gasdistribution chamber 18 trough the openings 20, are temporarily mixedwith the liquid phase above such chamber 18 and are collected again inthe sectors 24 of the further gas distribution chamber 23.

From here, the gaseous compounds are advantageously directly andindependently fed within each of said tubes 6′ intended forcondensation, through the connecting ducts 21, where they mix forreaction and condensation to carbamate with the liquid phasecontemporaneously entering such tubes 6′ through the annular spaces 22,in heat exchange relationship with the coolant flowing outside the tubebundle 5.

Also in this case, there is no mixing of the two phases just below thelower tube plate 8, so that formation of gas preferential paths, i.e.uneven distribution of the gaseous phase, is prevented.

The presence of the intermediate channels 25 between adjacent sectors 24for the passage thereinbetween of the liquid phase, advantageouslyallows an optimal distribution of the liquid phase above such sectors 24before entering the tubes 6′ intended for condensation.

The distance between adjacent sectors 24, i.e. the width of the channels25, is chosen in a way to impede gaseous compounds to flow in thechannels 25. To this aim, the carbamate condensation unit 1 preferablycomprises gas deflecting means 27 associated to the channels 25.

In the example of FIGS. 3-4, the gas deflecting means 25 areadvantageously obtained by providing the side walls 24 b of the sectors24 with different length and shape, so that once the sectors arearranged one beside the other, one of the two opposite side walls 24 bof adjacent sectors 24 is longer then the other and its free end 24 c iscurved towards and extend over the shorter side wall.

Preferably, the carbamate condensation unit 1 further comprises aplurality of deflecting baffles 28 arranged in the lower portion 11,between the sectors 24 and the lower tube plate 8, below said tubes 6″intended for recycle of the liquid phase. By doing so, it is possible tobetter control the flow direction of the liquid phase coming downwardlyfrom the tubes 6″ and the liquid phase coming upwardly through thechannels 25, to all advantage of the natural circulation of the liquidphase within the unit 1.

According to another embodiment of the present invention, the sectors 24are preferably in gas communication the ones with the others by means oftubular connectors (not shown) that advantageously allows an improvedand more homogeneous gas distribution of the gaseous compounds withinthe further gas distribution chamber 23. Moreover, the presence of suchtubular connectors also permits to strengthen the structure of thechamber 23.

With respect to the sectors 24, it should be noted that also the gasdistribution chamber 18 can be structured as the further gasdistribution chamber 23, i.e. divided in a plurality of contiguoussectors. In this case, means (not shown as being per se conventional)are provided between the duct 16 and the different sectors, foruniformly feeding to the latter the gaseous compounds.

The embodiments of FIGS. 1-4 are particularly advantageous for therevamping of pre-existing condensation units of the submerged type oreven of the film type.

In the latter units, the liquid phase is made to flow for gravity insidethe tubes of a tube bundle as a film of liquid in co-current with thegaseous compounds to be condensed.

In general, in pre-existing condensation units it is not possibleneither economically convenient to make structural modifications to thesame-, in particular to the shell.

Advantageously, thanks to the present invention, the pre-existingcarbamate condensation unit is provided in its lower portion with gasdistribution chamber(s) and connecting ducts for feeding,contemporaneously and independently, the gaseous phase and the liquidphase within each of the tubes of the heat exchange tube bundle intendedfor condensation, without the need of intervening onto the existingstructure of the shell and of the bottoms. By doing so, the efficiencyand the condensation yield of the unit are drastically increased.

Advantageously, the carbamate condensation method of the presentinvention can also be applied to submerged condensation units of thetype disclosed in WO 02/34382, wherein the predetermined number of tubesintended for carbamate condensation corresponds to the overall number oftubes of the tube bundle and the recycle of the liquid phase is obtainedthrough a structurally independent duct.

In this respect, it should be noted that the number and the arrangementof the tubes intended for condensation and of the tubes intended forrecycling of a portion of the condensed compounds given in the FIGS. 1-4are merely by way of non-limiting and explanatory example, and can bemodified depending on the required operating conditions or structure ofthe unit.

The invention thus conceived is susceptible to further embodiments andmodifications all of which are within the capabilities of the manskilled in the art and, as such, fall within the scope of protection ofthe invention itself, as defined by the following claims.

1. Method for carbamate condensation of a carbon dioxide/ammonia gaseous phase in a liquid phase in a condensation unit of the so-called submerged type comprising a heat exchange tube bundle having a predetermined number of tubes intended for carbamate condensation, characterized by the step of: feeding, contemporaneously and independently, said gaseous phase and said liquid phase within each of said tubes intended for condensation.
 2. Method according to claim 1, characterized in that it comprises the steps of: feeding said gaseous phase to a gas distribution chamber arranged within said condensation unit below said tube bundle; collecting said gaseous phase in said gas distribution chamber and feeding said gaseous phase within said tubes intended for carbamate condensation through a plurality of connecting ducts extending from said gas distribution chamber to said tubes intended for carbamate condensation.
 3. Method according to claim 1, characterized in that it comprises the steps of: feeding said gaseous phase to a gas distribution chamber arranged within said condensation unit below said tube bundle; collecting said gaseous phase in said gas distribution chamber and feeding said gaseous phase to a further gas distribution chamber above thereto; collecting said gaseous phase in said further gas distribution chamber and feeding said gaseous phase within said tubes intended for carbamate condensation through a plurality of connecting ducts extending from said further gas distribution chamber to said tubes intended for carbamate condensation.
 4. Method according to claim 2, characterizing in that it comprises the step of: feeding said liquid phase within said tubes intended for carbamate condensation through annular spaces defined between said tubes intended for condensation and said connecting ducts.
 5. Carbamate condensation unit of the submerged type for carbamate condensation of a carbon dioxide/ammonia gaseous phase in a liquid phase, comprising: a heat exchange tube bundle having a predetermined number of tubes intended for carbamate condensation at their interior; a gas distribution chamber for collecting said gas phase fed to said condensation unit; and a plurality of connecting ducts extending from said gas distribution chamber to the interior tubes intended for condensation, so as to obtain a direct gas communication between said chamber and said tubes.
 6. Carbamate condensation unit of the submerged type for carbamate condensation of a carbon dioxide/ammonia gaseous phase in a liquid phase, comprising: a heat exchange tube bundle having a predetermined number of tubes intended for carbamate condensation at their interior a gas distribution chamber for collecting said gas phase fed to said condensation unit arranged below said tube bundle; a further gas distribution chamber arranged between said gas distribution chamber and said tube bundle for collecting said gas phase coming from said gas distribution chamber; and a plurality of connecting ducts extending from said further gas distribution chamber to the interior said tubes intended for condensation, so as to obtain a direct gas communication between said further chamber and said tubes.
 7. Condensation unit according to claim 6, characterized in that said connecting ducts have a free upper end ending within and in proximity of a lower end of said tubes intended for condensation.
 8. Condensation unit according to claim 7, characterized in that said upper end of the connecting ducts has a diameter smaller than the diameter of said lower end of the tubes intended for condensation, so that an annular space is defined between said ducts and said tubes for the inlet thereto of the liquid phase.
 9. Condensation unit according to claim 6, characterized in that said further gas distribution chamber is divided in a plurality of sectors, contiguous and separated the one from the other so as to define intermediate channels for the passage of said liquid phase between said sectors.
 10. Condensation unit according to claim 9, characterized in that it further comprises gas deflecting means associated to said intermediate channels.
 11. Condensation unit according to claim 10, carbamate characterized in that said gas deflecting means are obtained by providing said sectors with side walls of different length and shape, so that once said sectors are arranged one beside the other within said unit, one of the two opposite side walls of adjacent sectors is longer then the other and has a free end curved towards and extendinger the opposite shorter side wall.
 12. Condensation unit according to claim 5, characterized in that it further comprises at least one deflecting baffle arranged between said gas distributing chamber and said tube bundle, below at least one tube of the tube bundle intended for recycling said liquid phase.
 13. Condensation unit according to claim 6, characterized in that it further comprises at least one deflecting baffle arranged between said further gas distribution chamber and said tube bundle, below at least one tube of the tube bundle intended for recycling said liquid phase.
 14. Condensation unit according to claim 9, characterized in that said sectors in gas communication the ones with the others by means of tubular connectors.
 15. Condensation unit according to claim 5, characterized in that said connecting ducts have a free upper end ending within and in proximity of a lower end of said tubes intended for condensation.
 16. Condensation unit according to claim 15, characterized in that said upper end of the connecting ducts has a diameter smaller than the diameter of said lower end of the tubes intended for condensation, so that an annular space is defined between said ducts and said tubes for the inlet thereto of the liquid phase. 